EP0805846B1 - Liquid detergent - Google Patents

Liquid detergent Download PDF

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Publication number
EP0805846B1
EP0805846B1 EP96901298A EP96901298A EP0805846B1 EP 0805846 B1 EP0805846 B1 EP 0805846B1 EP 96901298 A EP96901298 A EP 96901298A EP 96901298 A EP96901298 A EP 96901298A EP 0805846 B1 EP0805846 B1 EP 0805846B1
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EP
European Patent Office
Prior art keywords
weight
alkyl
fatty acid
detergent
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96901298A
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German (de)
French (fr)
Other versions
EP0805846A1 (en
Inventor
Ansgar Behler
Astrid Haferkamp
Kerstin Link
Amerigo Pastura
Nada Volf
Günther VOGT
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0805846A1 publication Critical patent/EP0805846A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to a low-foaming liquid detergent for washing textiles.
  • Liquid textile detergents are well known and are very popular with consumers. The main reasons for this are the dust-free applicability of liquid detergents and their easy dosing.
  • aqueous liquid detergents contain anionic and non-ionic surfactants as washing-active substances.
  • the anionic and nonionic surfactants used have proven to be very disadvantageous shown.
  • Liquid detergent compositions are e.g. B. in the European patent application 30 096 and the German patent application 42 27 046.
  • European patent application 30 096 describes non-aqueous liquid detergents liquid nonionic surfactants known, which in addition to builder substances also bleach in suspended May contain shape. If desired, anionic surfactants such as Alkylbenzenesulfonates, olefin sulfonates, alkyl sulfates or soap can be added. It will however, no precise details were given about the amounts and the form the anionic surfactants are introduced into the agents.
  • German patent application 42 27 046 describes a detergent mixture which is suitable for use as a detergent, kitchen and household cleaning agent, which as wash-active components are fatty acid esters of a polyoxyalkylene alkyl ether, alkylbenzenesulfonic acids, Alkyl ether sulfates, alkyl sulfates, ⁇ -sulfofatty acid esters, ⁇ -olefin sulfonic acids and optionally builder substances, enzymes, bleaching agents and others Contains additives.
  • alkyl polyglycosides As an ecologically particularly advantageous detergent substance in detergents and cleaning agents have the alkyl polyglycosides (APG's) and alkyl sulfates with a high proportion of compounds shown with 12 carbon atoms.
  • alkyl polyglycosides are strong in the recipe foaming surfactants and are therefore particularly suitable for products with a high Foaming power is desired, e.g. for manual dishwashing detergents or for shampoos, recommended.
  • EP-B-0 070 071 and EP-B-0 070 076 describe such high-foaming detergents and cleaning agents based on various APG-containing surfactant combinations. These surfactant combinations are not for use as a liquid detergent recommended.
  • Low-foaming liquid detergents are e.g. B. in Japanese Patent Application Laid-Open JP 58/217598.
  • the detergent compositions described therein contain alkoxylated fatty acid alkyl esters as a foam-inhibiting substance. Furthermore, usual contain anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants be.
  • the present invention has for its object to provide a liquid detergent, that meets the high demands on the washing performance of modern detergents, good ones biodegradability and low foaming.
  • a liquid detergent that meets the high demands on the washing performance of modern detergents, good ones biodegradability and low foaming.
  • Preferably on long-chain soaps or silicone or paraffin foam can be dispensed with.
  • the alkyl polyglycosides used in the liquid detergents according to the invention represent known substances, which according to the relevant procedures of preparative organic Chemistry can be obtained; representative of the documents EP 0 301 298 A1 and WO 90/3977.
  • the alkyl polyglycosides can be of sugar or sugar residues, i.e. Aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and derive the xylose.
  • the preferred alkyl polyglycosides are thus alkyl polyglucosides and Alkyl polyxylosides.
  • the index x in formula (I) indicates the degree of oligomerization (DP degree), i.e. the distribution of Mono- and oligoglycosides and stands for a number between 1 and 10.
  • the value x must be which are not necessarily a whole number in the agents according to the invention, they can mixtures of compounds with different degrees of oligomerization are also used be so that the value x for a certain alkyl polyglycoside determined analytically arithmetic size, which usually represents a fractional number.
  • the alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are lauryl, myristyl and cetyl alcohol and their technical mixtures. However, alkyl polyglycosides of the formula (I) are preferably used in which R 1 represents a carbon radical having 8 to 14, in particular 12 to 14, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis or as Ziegler alcohols.
  • the agents according to the invention preferably contain 3% by weight to 25% by weight, in particular 5% by weight to 20% by weight, of compounds having the formula (I).
  • the fatty acid alkyl ester alkoxylates of the formulas (II) and (III) used in the liquid detergents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol.
  • this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures.
  • fatty acid methyl ester alkoxylates produced in this way have relatively high OH numbers after the esterification, which can be problematic for some applications.
  • the fatty acid alkyl ester alkoxylates of the formulas (II) and (III) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained.
  • fatty acid alkyl ester alkoxylates of the formulas (II) and (III) which are formed by ethoxylation of fatty acid alkyl esters, ie in which AO in the formulas (II) and (III) for an ethylene oxide unit and R 3 for a short alkyl chain with 1 to 6, are preferably used Carbon atoms, in particular for a methyl, ethyl, propyl or butyl group or their isomers, where R 3 is preferably methyl.
  • the fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats or produced synthetically.
  • the partial glyceride alkoxylates of the formula (IV) are prepared by alkoxylation of triglycerides in the presence of glycerin.
  • liquid detergents according to the invention for removing lipophilic soiling are used, one preferably chooses fatty acid alkyl ester alkoxylates with in the invention Low level of ethoxylation range; are supposed to be hydrophilic soiling to be removed is the use of fatty acid alkyl ester ethoxylates in the invention Range of higher degree of ethoxylation appropriate.
  • the fatty acid alkyl ester alkoxylates of the formulas (11), (III) and (IV) are used in the inventive Average in amounts of 5 % By weight -. up to 20% by weight -. used.
  • Particularly suitable salts of the sulfuric acid monoesters, also referred to as fatty alkyl sulfates, in the liquid detergents according to the invention are the salts of the sulfuric acid monoesters of C 6 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and those of coconut oil, palm and Fatty alcohol mixtures obtained from palm kem oil, which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol.
  • Preferred mixtures are those in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , less than 3% by weight .-% on C 10 and less than 10 wt .-% are distributed on C 18 .
  • the proportion of fatty alkyl sulfates in the compositions is preferably more than 2% by weight to 15% by weight, particularly preferably 3% by weight. up to 8% by weight.
  • liquid detergents according to the invention can be further nonionic and anionic Contain surfactants.
  • nonionic surfactants may be selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettklapolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides and mixtures thereof, wherein the C 6 -C 18 -alkyl polyglycol ether are particularly preferred.
  • the nonionic surfactants can be present in a total amount of up to 60% by weight, preferably 15% by weight. up to 30% by weight, based on the total amount of the liquid detergent according to the invention.
  • Anionic surfactants which can additionally be present in the liquid detergent according to the invention can be selected from the group of C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, C 6 - C 18 -Alkylpolyglykolethersulfonate, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 18 fatty acid amide ether sulfates, C 6-18 alkyl carboxylates, fatty acid isethionates, NC 6 -C 18 acyl sarcosinates, NC 6 -C 18 acyl taurides and
  • Disalze is obtained by reaction of saturated or unsaturated, mainly based on natural raw materials
  • Fatty acids by reaction with sulfur trioxide and subsequent conversion into the alkali metal salts are obtained, the conversion of saturated fatty acids to disalts leads, which are sulfonated in ( ⁇ -position, during the implementation of unsaturated fatty acids Disalze results, which are predominantly internal to the formerly double-bonded carbon atoms are sulfonated.
  • These compounds can be easily incorporated into liquid detergents.
  • Preferred Disalze derive from fatty acids or fatty acid mixtures, especially natural ones Origin, which has a C chain length between 8 and 18 and preferably between 12 and 18 have.
  • the anionic surfactants can be present in a total amount of up to 40% by weight, preferably of 3 wt .-% to 20 wt .-%, based on the total weight of the liquid detergent.
  • the weight ratio of the nonionic surfactants to the anionic surfactants is, for example between 3.5: 1 and 1: 2.0.
  • Formulations rich in nonionic surfactants are particularly advantageous with a weight ratio of nonionic surfactant: anionic surfactant between 3.5: 1 and 1.3: 1 and especially 3.2: 1 to 2.4: 1 and anionic surfactant rich formulations with a weight ratio
  • the nonionic surfactant-rich agents can be from 3% to 10% by weight of anionic surfactant and Contain 10 wt% to 40 wt% nonionic surfactants, while the anionic surfactant-rich agents are preferred 10 wt% to 20 wt% anionic surfactants and 5 wt% to 30 wt% nonionic surfactants contain.
  • Preferred agents have a viscosity between 150 and 5000 mpas (20 ° C, shear rate 30 / s).
  • the desired viscosity of the agent can be achieved by adding water and / or organic solvents or by adding a combination of organic Solvents and thickeners can be adjusted.
  • organic Solvents are all monohydric or polyhydric alcohols.
  • To be favoured Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight and branched chain butanol, glycerol and mixtures of the alcohols mentioned.
  • Other preferred alcohols are polyethylene glycols with a relative molecular weight less than 2,000.
  • polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and with polyethylene glycol a relative molecular weight between 400 and 600 and in amounts of 5 to 25 wt .-% preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example Ethanol, and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, the inventive Liquid detergents can contain 8 to 12% by weight of such a mixture.
  • suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Hardened castor oil salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 up to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and also polymeric compounds.
  • agents according to the invention can also contain peroxy bleaches which are in aqueous Recipes are protected accordingly from the attack of water.
  • the liquid detergents according to the invention can contain other solids in addition to those mentioned contained in dispersed form.
  • the ratio of fixed parts: liquid parts do not exceed the value 40:60.
  • the dispersed solids preferably have an average grain size of 1 to 10 ⁇ m and especially 1 to 5 ⁇ m (measurement method: Coulter counter or Fraunhofer diffraction, volume distribution).
  • the funds can be up to to 6 wt .-% contain particles with a size in the range of 0.2 to 2 mm, without the Stability of funds is compromised.
  • the agents preferably contain max. 5% by weight Granules of this size.
  • the agents can include other conventional components such as inorganic and organic Builders, carbonates, silicates, hydroxides, foam inhibitors, optical brighteners, Contain enzymes as well as colors and fragrances.
  • Neutral or in particular are suitable as organic and inorganic builders alkaline reacting salts that can precipitate calcium ions or bind them in a complex manner.
  • Suitable and in particular ecologically harmless builder substances such as fine crystalline synthetic water-containing zeolites of the type NaA, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) are preferred Use.
  • Your average particle size (measurement method: Coulter Counter, volume distribution) is usually in the range from 1 to 10 ⁇ m and preferably in the range from 1 up to 5 ⁇ m.
  • Layered silicates are preferably used in non-aqueous systems. Zeolite and the layered silicates can be used in an amount of up to 20% by weight.
  • Usable organic builders are, for example, the preferred ones in the form of their sodium salts used polycarboxylic acids, such as citric acid, and nitrilotriacetate (NTA), so far such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetate
  • these polymeric carboxylates and their salts are also used. These include, for example the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular Copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% Maleic acid and also polyvinyl pyrrolidone and urethanes.
  • the relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • Especially water-soluble polyacrylates are also suitable, for example with about 1% of a polyallyl ether of sucrose are cross-linked and have a relative molecular weight above own a million. Examples of this are those under the name Carbopol® 940 and 941 available polymers.
  • the crosslinked polyacrylates are used in amounts not exceeding 1% by weight, preferably used in amounts of 0.2 to 0.7 wt .-%. These frameworks can can be used in amounts of up to 5% by weight.
  • the agents according to the invention can contain other non-surfactant-like foam inhibitors included, although these are not required in the agents according to the invention in order to To improve foam behavior.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica and Paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. With Mixtures of different foam inhibitors can also advantageously be used, e.g. such made of silicone oil, paraffin oil or wax.
  • the foam inhibitors are preferably attached to one granular, water-soluble or dispersible carrier substance bound.
  • the liquid detergents contain, for example, derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts, which work well into the dispersion to let.
  • the maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.
  • Enzymes come from the class of proteases, lipases, amylases or their Mixtures in question. Their proportion can be 0.2 to 1% by weight. The enzymes can on carriers adsorbed and / or embedded in coating substances.
  • the salts of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be used.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • the agent according to the invention contains 3% by weight to 30% % By weight nonionic surfactants, 3% by weight to 15% by weight anionic surfactants up to 2% by weight Thickeners, up to 15% by weight of framework substances, 0.05% by weight to 0.2% by weight of optical brighteners and 0.3 wt% to 1.5 wt% enzymes.
  • the liquid detergents can be mixed, for example, by simple mixing or by wet grinding the mixture of alkyl polyglycosides, fatty acid alkyl ester alkoxylates and sulfuric acid monoester salts be preserved.
  • further surfactants, solvents, if Desired thickener, and optionally a defoamer placed in a reactor with is provided with a stirring system and mixed together.
  • others can Components of the agent are added individually or in a mixture.
  • the Wet grinding of the dispersion at temperatures up to a maximum of 70 ° C, but preferably at Temperatures up to 32 ° C and especially at room temperature.
  • the duration of the grinding is a maximum of 30 minutes.
  • the grinding is preferably carried out in significantly shorter times, for example between 3 and 10 minutes. Are particularly suitable for this purpose high-speed and finely ground colloid and annular gap ball mills. Possibly Triacetin present is preferably added to the dispersion after grinding.
  • the pour point of the agents is preferably below 10 ° C. and in particular below of 6 ° C.
  • the pH of the compositions is between 6 and 10 and preferably between 7.5 and 9.5.
  • the agents were at room temperature as well as at 40 ° C for at least 3 months stable. In the case of approaches that had been stored for a long time, there was no weaning even after 12 months observed.
  • the agents used according to the invention contain optical brighteners. Although the use of brightener-containing agents is preferred, agents which are free from optical brighteners can also be used in the process according to the invention. Except for this exception, preferred forms of use are those in which the agents designated above as preferred are used.
  • Preferred uses are therefore those in which the alkyl polyglycoside with the formula IR 1 represents an alkyl group with 8 to 14 carbon atoms and in the fatty acid alkyl ester alkoxylate with the formula II or III AO represents an ethylene oxide unit and R 3 represents a methyl group or in which other nonionic groups Surfactants selected from the group of C 6 -C 18 alkyl polyglycol ethers, sugar esters, C 6 -C 18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides and mixtures thereof in an amount of up to 60% by weight, based on the total agent, are included, the nonionic surfactant being selected from the group of the C 6 -C 18 -alkyl polyglycol ethers in particularly preferred uses.
  • the agent to be used contains further anionic surfactants selected from the group C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates , glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 18 fatty acid amide ether sulfates, C 6 -C 18 alkyl carboxylates, fatty acid isethionates, NC 6 -C 18 acyl sarcosinates, NC 6 - C 18 acyl taurides, C 6 -C
  • the anionic surfactant is selected from the group of the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and mixtures thereof.
  • the agent used contains 3% by weight to 30% % By weight nonionic surfactants, 2% by weight to 15% by weight anionic surfactants up to 2% by weight Thickeners, up to 15% by weight of framework substances, 0.05% by weight to 0.2% by weight of optical Brightener and 0.3 wt% to 1.5 wt% enzymes.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Die Erfindung betrifft ein schaumarmes Flüssigwaschmittel zum Waschen von Textilien.The invention relates to a low-foaming liquid detergent for washing textiles.

Flüssige Textilwaschmittel sind hinreichend bekannt und sind beim Verbraucher sehr beliebt. Gründe hierfür sind vor allem die staubfreie Anwendbarkeit der Flüssigwaschmittel sowie ihre leichte Dosierbarkeit. Im allgemeinen enthalten wäßrige Flüssigwaschmittel anionische und nichtionische Tenside als waschaktive Substanzen. Das hohe Schaumvermögen der eingesetzten anionischen und nichtionischen Tenside hat sich jedoch als sehr nachteilig gezeigt. Der Verbraucher möchte zwar zum Nachweis der Wirksamkeit der Waschmittel zu Beginn des Waschvorgangs, entweder im Handwaschbecken oder bei der maschinellen Wäsche, ein gewisses Schäumen wahrnehmen, der Schaum soll dann jedoch anschließend möglichst rasch zusamenfallen, damit nach einer möglichst geringen Anzahl von Spülgängen kein Schaum mehr sichtbar ist.Liquid textile detergents are well known and are very popular with consumers. The main reasons for this are the dust-free applicability of liquid detergents and their easy dosing. In general, aqueous liquid detergents contain anionic and non-ionic surfactants as washing-active substances. The high foaming power of the However, the anionic and nonionic surfactants used have proven to be very disadvantageous shown. The consumer wants to prove the effectiveness of the detergent Start of the washing process, either in the hand wash basin or by machine Wash, perceive a certain amount of foaming, but the foam should then follow collapse as quickly as possible, so after the smallest possible number of rinse cycles no more foam is visible.

Um dem vermehrten Wunsch nach geringerem Schaumvermögen nachzukommen, ist es zwar möglich, den Tensidgehalt der Produkte zu senken, was jedoch auch zu einem erheblichen Verlust der Waschleistung führt.To meet the increased desire for less foaming, it is possible to lower the surfactant content of the products, but this also leads to a significant Loss of washing performance results.

Flüssige Waschmittelzusammensetzungen werden z. B. in der europäischen Patentanmeldung 30 096 und der deutschen Patentanmeldung 42 27 046 beschrieben.Liquid detergent compositions are e.g. B. in the European patent application 30 096 and the German patent application 42 27 046.

Aus der europäischen Patentanmeldung 30 096 sind nicht-wäßrige Flüssigwaschmittel aus flüssigen Niotensiden bekannt, die neben Buildersubstanzen auch Bleichmittel in suspendierter Form enthalten können. Falls erwünscht, können den Mitteln anionische Tenside, wie Alkylbenzolsulfonate, Olefinsulfonate, Alkylsulfate oder Seife, zugesetzt werden. Es werden jedoch keine genaueren Angaben darüber gemacht, in welchen Mengen und in welcher Form die anionische Tenside in die Mittel eingebracht werden. European patent application 30 096 describes non-aqueous liquid detergents liquid nonionic surfactants known, which in addition to builder substances also bleach in suspended May contain shape. If desired, anionic surfactants such as Alkylbenzenesulfonates, olefin sulfonates, alkyl sulfates or soap can be added. It will however, no precise details were given about the amounts and the form the anionic surfactants are introduced into the agents.

In der deutschen Patentanmeldung 42 27 046 wird eine Detergentienmischung beschneben, die zur Verwendung als Waschmittel, Küchen- und Haushaltsreinigungsmittel geeignet ist, welche als waschaktive Komponenten Fettsäureester eines Polyoxyalkylenalkylethers, Alkylbenzolsulfonsäuren, Alkylethersulfate, Alkylsulfate, α-Sulfofettsäureester, α-Olefinsulfonsäuren und gegebenenfalls Gerüstsubstanzen, Enzyme, Bleichmittel und weitere Additive enthält.German patent application 42 27 046 describes a detergent mixture which is suitable for use as a detergent, kitchen and household cleaning agent, which as wash-active components are fatty acid esters of a polyoxyalkylene alkyl ether, alkylbenzenesulfonic acids, Alkyl ether sulfates, alkyl sulfates, α-sulfofatty acid esters, α-olefin sulfonic acids and optionally builder substances, enzymes, bleaching agents and others Contains additives.

Als ökologisch besonders vorteilhafte waschaktive Substanz in Wasch- und Reinigungsmitteln haben sich die Alkylpolyglycoside (APG's) und Alkylsulfate mit einem hohen Anteil an Verbindungen mit 12 Kohlenstoffatomen gezeigt. Alkylpolyglycoside sind jedoch in Rezeptur stark schäumende Tenside und werden deshalb insbesondere für Produkte, bei denen ein hohes Schaumvermögen erwünscht ist, also z.B. für manuell anzuwendende Geschirrspülmittel oder für Haarwaschmittel, empfohlen. EP-B-0 070 071 und EP-B-0 070 076 beschreiben derartige hochschäumende Wasch- und Reinigungsmittel auf Basis verschiedener APG-haltiger Tensidkombinationen. Diese Tensidkombinationen werden nicht für die Anwendung als Flüssigwaschmittel empfohlen.As an ecologically particularly advantageous detergent substance in detergents and cleaning agents have the alkyl polyglycosides (APG's) and alkyl sulfates with a high proportion of compounds shown with 12 carbon atoms. However, alkyl polyglycosides are strong in the recipe foaming surfactants and are therefore particularly suitable for products with a high Foaming power is desired, e.g. for manual dishwashing detergents or for shampoos, recommended. EP-B-0 070 071 and EP-B-0 070 076 describe such high-foaming detergents and cleaning agents based on various APG-containing surfactant combinations. These surfactant combinations are not for use as a liquid detergent recommended.

Niedrig schäumende Flüssigwaschmittel werden z. B. in der japanischen Offenlegungsschrift JP 58/217598 beschrieben. Die dort beschriebenen Waschmittelzusammensetzungen enthalten als schaumhemende Substanz alkoxylierte Fettsäurealkylester. Ferner können übliche anionische Tenside, nichtionische Tenside, kationische Tenside und amphotere Tenside enthalten sein.Low-foaming liquid detergents are e.g. B. in Japanese Patent Application Laid-Open JP 58/217598. The detergent compositions described therein contain alkoxylated fatty acid alkyl esters as a foam-inhibiting substance. Furthermore, usual contain anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants be.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Flüssigwaschmittel bereitzustellen, das den hohen Anforderungen an die Waschleistung modemer Waschmittel genügt, gute biologische Abbaubarkeit und ein schwaches Schäumvermögen besitzt. Bevorzugt soll auf langkettige Seifen oder auch Silicon- oder Paraffinentschäumem verzichtet werden können.The present invention has for its object to provide a liquid detergent, that meets the high demands on the washing performance of modern detergents, good ones biodegradability and low foaming. Preferably on long-chain soaps or silicone or paraffin foam can be dispensed with.

Gegenstand der Erfindung ist dementsprechend ein Flüssigwaschmittel, welches enthält:
0,1 Gew.-% bis 40 Gew.-% mindestens eines Alkylpolyglycosids mit der Formel I R1-O-[Z]x

  • worin R1 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 8 bis 18 C-Atomen, Z einen Zuckerrest, vorzugsweise einen Glucose- oder Xylose-Rest und x eine ganze Zahl von 1 bis 10 darstellt,
    5 Gew.-% bis 20 Gew.-% mindestens eines Fettsäurealkylesteralkoxylats mit der Formel II, III oder IV R2 -CO2-(AO)y-R3 R3-CO2-(AO)y-R2
    Figure 00030001
    worin
  • R2 für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 7 bis 17 C-Atomen,
  • R3 für eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 C-Atomen steht,
  • R4, R5 und R6 gleich oder verschieden sein können und für Wasserstoff oder
    Figure 00030002
    stehen, worin R7 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen sein kann, mit der Maßgabe, daß R4, R5 und R6 nicht gleichzeitig Wasserstoff sind, AO für eine C2-C4-Alkylenoxydeinheit steht, y für eine Zahl von 1 bis 30, vorzugweise 5 bis 25, insbesondere 9 bis 18, und n, o und p gleich oder verschieden seien können und für eine Zahl von 1 bis 60, vorzugsweise 1 bis 30, insbesondere 3 bis 12, stehen, und mehr als 2 Gew.-% bis 20 Gew.-% mindestens eines Salzes von Schwefelsäuremonoestern der C6- bis C18-Fettalkohole und 0,02 bis 0,5 Gew.-% optischen Aufheller.
    • The invention accordingly relates to a liquid detergent which contains:
    0.1% to 40% by weight of at least one alkyl polyglycoside with the formula I. R 1 -O- [Z] x
  • in which R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or xylose residue and x is an integer from 1 to 10,
    5% by weight to 20% by weight of at least one fatty acid alkyl ester alkoxylate with the formula II, III or IV R 2 -CO 2 - (AO) y -R 3 R 3 -CO 2 - (AO) y -R 2
    Figure 00030001
    wherein
  • R 2 represents a branched or straight-chain, saturated or unsaturated alkyl group with 7 to 17 C atoms,
  • R 3 represents a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms,
  • R 4 , R 5 and R 6 may be the same or different and represent hydrogen or
    Figure 00030002
    are in which R 7 can be a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 carbon atoms, with the proviso that R 4 , R 5 and R 6 are not simultaneously hydrogen, AO for a C 2 -C 4 Alkylene oxide unit, y is a number from 1 to 30, preferably 5 to 25, in particular 9 to 18, and n, o and p can be identical or different and a number from 1 to 60, preferably 1 to 30, in particular 3 to 12, and more than 2% by weight to 20% by weight of at least one salt of sulfuric acid monoesters of C 6 to C 18 fatty alcohols and 0.02 to 0.5% by weight of optical brighteners.

    • Die in den erfindungsgemäßen Flüssigwaschmitteln eingesetzten Alkylpolyglycoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können; stellvertretend sei hier auf die Schriften EP 0 301 298 A1 und WO 90/3977 verwiesen. Die Alkylpolyglycoside können sich von Zuckem bzw. Zuckerresten, d.h. Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose und der Xylose ableiten. Die bevorzugten Alkylpolyglycoside sind somit Alkylpolyglucoside und Alkylpolyxyloside.The alkyl polyglycosides used in the liquid detergents according to the invention represent known substances, which according to the relevant procedures of preparative organic Chemistry can be obtained; representative of the documents EP 0 301 298 A1 and WO 90/3977. The alkyl polyglycosides can be of sugar or sugar residues, i.e. Aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and derive the xylose. The preferred alkyl polyglycosides are thus alkyl polyglucosides and Alkyl polyxylosides.

    Der Index x in der Formel (I) gibt den Oligomerisierungsgrad (DP-Grad), d.h. die Verteilung von Mono- und Oligoglycosiden an und steht für eine Zahl zwischen 1 und 10. Der Wert x muß für die in den erfindungsgemäßen Mitteln nicht notwendigerweise einge ganze Zahl sein, es können auch Gemische von Verbindungen mit unterschiedlichem Oligomerisierungsgrad eingesetzt werden, so daß der Wert x für ein bestimmtes Alkylpolyglycosid eine analytisch ermittelte rechnerische Größe ist, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylpolyglycoside mit einem mittleren Oligomerisierungsgrad von 1,1 bis 3,0, vorzugsweise 1,1 bis 1,7 eingesetzt.The index x in formula (I) indicates the degree of oligomerization (DP degree), i.e. the distribution of Mono- and oligoglycosides and stands for a number between 1 and 10. The value x must be which are not necessarily a whole number in the agents according to the invention, they can mixtures of compounds with different degrees of oligomerization are also used be so that the value x for a certain alkyl polyglycoside determined analytically arithmetic size, which usually represents a fractional number. Preferably be Alkyl polyglycosides with an average degree of oligomerization of 1.1 to 3.0, preferably 1.1 to 1.7 used.

    Der Alkylrest R1 in der Formel (I) kann sich von primären verzweigten und unverzweigten Alkoholen mit 8 bis 18 Kohlenstoffatomen ableiten. Typische Beispiele sind Lauryl-, Myristyl- und Cetylalkohol sowie deren technische Gemische. Vorzugsweise werden jedoch Alkylpolyglycoside der Formel (I) eingesetzt, in denen Rl einen Kohlenstoffrest mit 8 bis 14, insbesondere 12 bis 14 Kohlenstoffatomen, darstellt. Typische Beispiele sind neben Laurylalkohol insbesondere Caprylalkohol und Caprinalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestem oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen-Oxosynthese oder als Ziegleralkohole anfallen. Die erfindungsgemäßen Mittel enthalten bevorzugt 3 Gew.-% bis 25 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% Verbindungen mit der Formel (I).The alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are lauryl, myristyl and cetyl alcohol and their technical mixtures. However, alkyl polyglycosides of the formula (I) are preferably used in which R 1 represents a carbon radical having 8 to 14, in particular 12 to 14, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis or as Ziegler alcohols. The agents according to the invention preferably contain 3% by weight to 25% by weight, in particular 5% by weight to 20% by weight, of compounds having the formula (I).

    Die in den erfindungsgemäßen Flüssigwaschmitteln eingesetzten Fettsäurealkylesteralkoxylate der Formeln (II) und (III) können durch konventionelle Methoden hergestellt werden, wie z.B. durch Veresterung von Fettsäurederivaten mit alkoxyliertem Methanol. Dieses Verfahren ist jedoch mit einigen Nachteilen verbunden, es verläuft zweistufig, die Veresterung dauert sehr lange und die Produkte sind durch die hohen Reaktionstemperaturen gefärbt. Außerdem besitzen solchermaßen hergestellte Fettsäuremethylesteralkoxylate nach der Veresterung relativ hohe OH-Zahlen, was für manche Anwendungen problematisch sein kann. Vorzugsweise werden die Fettsäurealkylesteralkoxylate der Formeln (II) und (III) durch eine heterogen katalysierte Direktalkoxylierung von Fettsäurealkylester mit Alkylenoxid, insbesondere Ethylenoxid, hergestellt. Dieses Syntheseverfahren ist in WO 90/13533 und WO 91/15441 ausführlich beschrieben. Die dabei entstehenden Produkte zeichnen sich eine niednge OH-Zahl aus, die Reaktion wird einstufig durchgeführt und man erhält hellfarbige Produkte. Vorzugsweise werden solche Fettsäurealkylesteralkoxylate der Formeln (II) und (III) eingesetzt, die durch Ethoxylierung von Fettsäurealkylestem entstehen, d.h. in denen AO in der Formeln (II) und (III) für eine Ethylenoxideinheit und R3 für eine kurze Alkylkette mit 1 bis 6 Kohlenstoffatomen, insbesondere für eine Methyl-, Ethyl-, Propyl- oder Butylgruppe oder deren Isomeren steht, wobei R3 bevorzugt Methyl ist. Die als Ausgangsstoffe dienenden Fettsäurealkylester können sowohl aus natürlichen Ölen und Fetten gewonnen als auch auf synthetischem Wege hergestellt werden. Die Partialglyceridalkoxylate der Formel (IV) werden durch Alkoxylierung von Triglyceriden in Gegenwart von Glycerin hergestellt.The fatty acid alkyl ester alkoxylates of the formulas (II) and (III) used in the liquid detergents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol. However, this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures. In addition, fatty acid methyl ester alkoxylates produced in this way have relatively high OH numbers after the esterification, which can be problematic for some applications. The fatty acid alkyl ester alkoxylates of the formulas (II) and (III) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formulas (II) and (III) which are formed by ethoxylation of fatty acid alkyl esters, ie in which AO in the formulas (II) and (III) for an ethylene oxide unit and R 3 for a short alkyl chain with 1 to 6, are preferably used Carbon atoms, in particular for a methyl, ethyl, propyl or butyl group or their isomers, where R 3 is preferably methyl. The fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats or produced synthetically. The partial glyceride alkoxylates of the formula (IV) are prepared by alkoxylation of triglycerides in the presence of glycerin.

    Sollen die erfindungsgemäßen Flüssigwaschmittel zur Entfernung lipophiler Anschmutzungen verwendet werden, wählt man bevorzugt Fettsäurealkylesteralkoxylate mit im erfindungsgemäßen Bereich liegendem niedrigen Ethoxylierungsgrad; sollen hydrophile Anschmutzungen entfernt werden, ist der Einsatz von Fettsäurealkyesterethoxylaten mit im erfindungsgemäßen Bereich liegenden höheren Ethoxylierungsgrad zweckmäßig.Are the liquid detergents according to the invention for removing lipophilic soiling are used, one preferably chooses fatty acid alkyl ester alkoxylates with in the invention Low level of ethoxylation range; are supposed to be hydrophilic soiling to be removed is the use of fatty acid alkyl ester ethoxylates in the invention Range of higher degree of ethoxylation appropriate.

    Die Fettsäurealkylesteralkoxylate der Formeln (11), (III) und (IV) werden in den erfindungsgemäßen Mitteln in Mengen von 5 Gew.-%-. bis 20 Gew.-%-. eingesetzt.The fatty acid alkyl ester alkoxylates of the formulas (11), (III) and (IV) are used in the inventive Average in amounts of 5 % By weight -. up to 20% by weight -. used.

    Als in den erfindungsgemäßen Flüssigwaschmitteln eingesetzten Salze der Schwefelsäuremonoester, auch als Fettalkylsulfate bezeichnet, eignen sich besonders die Salze der Schwefelsäuremonoester der C6-C18-Fettalkohole, wie Lauryl-, Myristyl-, Cetylalkohol- oder Stearylalkohol und der aus Kokosöl, Palm- und Palmkemöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. an Oleylalkohol, enthalten können. Bevorzugte Gemische sind solche, in denen der Anteil der Alkylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf C16, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C18 verteilt sind. Der Anteil an Fettalkylsulfaten in den Mitteln beträgt vorzugsweise mehr als 2 Gew.-% bis 15 Gew.-%, besonders bevorzugt 3 Gew.-%,. bis 8 Gew.-%.Particularly suitable salts of the sulfuric acid monoesters, also referred to as fatty alkyl sulfates, in the liquid detergents according to the invention are the salts of the sulfuric acid monoesters of C 6 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and those of coconut oil, palm and Fatty alcohol mixtures obtained from palm kem oil, which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol. Preferred mixtures are those in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , less than 3% by weight .-% on C 10 and less than 10 wt .-% are distributed on C 18 . The proportion of fatty alkyl sulfates in the compositions is preferably more than 2% by weight to 15% by weight, particularly preferably 3% by weight. up to 8% by weight.

    Die erfindungsgemäßen Flüssigwaschmittel können weitere nichtionische und anionische Tenside enthalten.The liquid detergents according to the invention can be further nonionic and anionic Contain surfactants.

    Weitere nichtionische Tenside können ausgewählt werden aus der Gruppe der C6-C18-Alkylpolyglykolether, Zuckerester, C6-C18-Fettsäurepolyglykolether, Sorbitanfettsäureester, C6-C18-Fettsäurepartialglyceride sowie deren Mischungen, wobei die C6-C18-Alkylpolyglykolether besonders bevorzugt sind. Die nichtionischen Tenside können in einer Gesamtmenge von bis zu 60 Gew.-%, bevorzugt 15 Gew.-%. bis 30 Gew.-%, bezogen auf die Gesamtmenge des erfindungsgemäßen Flüssigwaschmittels, enthalten sein.Other nonionic surfactants may be selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettsäurepolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides and mixtures thereof, wherein the C 6 -C 18 -alkyl polyglycol ether are particularly preferred. The nonionic surfactants can be present in a total amount of up to 60% by weight, preferably 15% by weight. up to 30% by weight, based on the total amount of the liquid detergent according to the invention.

    Anionische Tenside, die zusätzlich im erfindungsgemäßen Flüssigwaschmittel enthalten sein können, können ausgewählt sein aus der Gruppe der C6-C18-Alkylbenzolsulfonate, C6-C18-Alkansulfonate, C6-C18-Alkylpolyglykolethersulfate, α-Olefinsulfonate, C6-C18-Alkylpolyglykolethersulfonate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Seifen, Amidseifen, C6-C18-Fettsäureamid-Ethersulfate,C6-18-Alkylcarboxylate, Fettsäureisethionate, N-C6-C18-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride und -Methyltauride, C6-C18-Alkyloligoglucosidsulfate, C6-C18-Alkylphosphate sowie deren Mischungen. Besonders bevorzugt werden C6-C18-Alkylpolyglykolethersulfate, Seifen und C6-C18-Alkansulfonate sowie deren Mischungen eingesetzt.Anionic surfactants which can additionally be present in the liquid detergent according to the invention can be selected from the group of C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl polyglycol ether sulfates, α-olefin sulfonates, C 6 - C 18 -Alkylpolyglykolethersulfonate, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 18 fatty acid amide ether sulfates, C 6-18 alkyl carboxylates, fatty acid isethionates, NC 6 -C 18 acyl sarcosinates, NC 6 -C 18 acyl taurides and methyl taurides, C 6 -C 18 alkyl oligoglucoside sulfates, C 6 -C 18 alkyl phosphates and mixtures thereof. C 6 -C 18 -Alkylpolyglycol ether sulfates, soaps and C 6 -C 18 -alkanesulfonates and mixtures thereof are particularly preferably used.

    Weitere bevorzugte anionische Bestandteile sind die sogenannten Disalze, welche durch Umsetzung von gesättigten oder ungesättigten, überwiegend auf natürlichen Rohstoffen basierenden Fettsäuren durch Umsetzung mit Schwefeltrioxid und anschließende Überführung in die Alkalizetallsalze erhalten werden, wobei die Umsetzung gesättigter Fettsäuren zu Disalzen führt, die in (α-Stellung sulfoniert sind, während die Umsetzung ungesättigter Fettsäuren Disalze ergibt, die überwiegend innenständig an den ehemals doppeltgebundenen C-Atomen sulfoniert sind. Diese Verbindungen lassen sich gut in Flüssigwaschmittel einarbeiten. Bevorzugte Disalze leiten sich von Fettsäuren bzw. Fettsäuregemischen insbesondere natürlichen Ursprungs ab, die eine C-Kettenlänge zwischen 8 und 18 und vorzugsweise zwischen 12 und 18 aufweisen.Further preferred anionic components are the so-called disalts, which are obtained by reaction of saturated or unsaturated, mainly based on natural raw materials Fatty acids by reaction with sulfur trioxide and subsequent conversion into the alkali metal salts are obtained, the conversion of saturated fatty acids to disalts leads, which are sulfonated in (α-position, during the implementation of unsaturated fatty acids Disalze results, which are predominantly internal to the formerly double-bonded carbon atoms are sulfonated. These compounds can be easily incorporated into liquid detergents. Preferred Disalze derive from fatty acids or fatty acid mixtures, especially natural ones Origin, which has a C chain length between 8 and 18 and preferably between 12 and 18 have.

    Die anionischen Tenside können in einer Gesamtmenge von bis zu 40 Gew.-%, bevorzugt von 3 Gew.-% bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Flüssigwaschmittels voriiegen.The anionic surfactants can be present in a total amount of up to 40% by weight, preferably of 3 wt .-% to 20 wt .-%, based on the total weight of the liquid detergent.

    Das Gewichtsverhältnis der nichtionischen Tenside zu den anionischen Tensiden beträgt beispielsweise zwischen 3,5 : 1 und 1 : 2,0. Mit besonderem Vorteil werden Niotensid-reiche Formulierungen mit einem Gewichtsverhältnis Niotensid : Aniontensid zwischen 3,5 : 1 und 1,3 : 1 und insbesondere 3,2 : 1 bis 2,4 : 1 und Aniontensid-reiche Formulierungen mit einem Gewichtsverhältnis Niotensid : Aniontensid von 1 : 1,1 bis 1 : 2,0 und insbesondere 1 : 1,1 bis 1 : 1,7 eingesetzt. Die Niotensid-reichen Mittel können 3 Gew.-% bis 10 Gew.-% Aniontensid und 10 Gew.-% bis 40 Gew.-% Niotenside enthalten, während die Aniontensid-reichen Mittel vorzugsweise 10 Gew.-% bis 20 Gew.-% Aniontenside und 5 Gew.-% bis 30 Gew.-% Niotenside enthalten.The weight ratio of the nonionic surfactants to the anionic surfactants is, for example between 3.5: 1 and 1: 2.0. Formulations rich in nonionic surfactants are particularly advantageous with a weight ratio of nonionic surfactant: anionic surfactant between 3.5: 1 and 1.3: 1 and especially 3.2: 1 to 2.4: 1 and anionic surfactant rich formulations with a weight ratio Nonionic surfactant: anionic surfactant from 1: 1.1 to 1: 2.0 and in particular 1: 1.1 to 1: 1.7 used. The nonionic surfactant-rich agents can be from 3% to 10% by weight of anionic surfactant and Contain 10 wt% to 40 wt% nonionic surfactants, while the anionic surfactant-rich agents are preferred 10 wt% to 20 wt% anionic surfactants and 5 wt% to 30 wt% nonionic surfactants contain.

    Bevorzugte Mittel besitzen eine Viskosität zwischen 150 und 5 000 mpas (20°C, Schergeschwindigkeit 30/s). Die gewünschte Viskosität der Mittel kann durch die Zugabe von Wasser und/oder organischen Lösungsmitteln oder durch die Zugabe einer Kombination aus organischen Lösungsmitteln und Verdickungsmitteln eingestellt werden. Prinzipiell kommen als organische Lösungsmittel alle ein- oder mehrwertigen Alkohole in Betracht. Bevorzugt werden Alkohole mit 1 bis 4 Kohlenstoffatomen wie Methanol, Ethanol, Propanol, Isopropanol, gerad- und verzweigtkettiges Butanol, Glycerin und Mischungen aus den genannten Alkoholen eingesetzt. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2 000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 und in Mengen von 5 bis 25 Gew.-% bevorzugt. Eine vorteilhafte Mischung aus Lösungsmitteln besteht aus monomerem Alkohol, beispielsweise Ethanol, und Polyethylenglykol im Verhältnis 0,5 : 1 bis 1,2 : 1, wobei die erfindungsgemäßen Flüssigwaschmittel 8 bis 12 Gew.-% einer solchen Mischung enthalten können. Weitere geeignete Lösungsmittel sind beispielsweise Triacetin (Glycerintriacetat) und 1-Methoxy-2-propanol. Preferred agents have a viscosity between 150 and 5000 mpas (20 ° C, shear rate 30 / s). The desired viscosity of the agent can be achieved by adding water and / or organic solvents or by adding a combination of organic Solvents and thickeners can be adjusted. In principle come as organic Solvents are all monohydric or polyhydric alcohols. To be favoured Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight and branched chain butanol, glycerol and mixtures of the alcohols mentioned. Other preferred alcohols are polyethylene glycols with a relative molecular weight less than 2,000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts up to 45% by weight and with polyethylene glycol a relative molecular weight between 400 and 600 and in amounts of 5 to 25 wt .-% preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example Ethanol, and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, the inventive Liquid detergents can contain 8 to 12% by weight of such a mixture. Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

    Als Verdickungsmittel werden bevorzugt gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder Kalium-Salze der Behensäure, sowie polymere Verbindungen eingesetzt.Hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 up to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and also polymeric compounds.

    Desweiteren können die erfindungsgemäßen Mittel auch Peroxybleichmittel, die in wäßrigen Rezepturen entsprechend vor dem Angriff des Wassers geschützt sind, enthalten sein.Furthermore, the agents according to the invention can also contain peroxy bleaches which are in aqueous Recipes are protected accordingly from the attack of water.

    Die erfindungsgemäßen Flüssigwaschmittel können außer den genannten noch weitere Feststoffe in dispergierter Form enthalten. Dabei soll das Verhältnis feste Anteile : flüssigen Anteilen den Wert 40 : 60 nicht überschreiten. Vorzugsweise besitzen die dispergierten Feststoffe eine mittlere Komgröße von 1 bis 10 µm und insbesondere von 1 bis 5 µm (Meßmethode: Coulter Counter oder Fraunhofer-Beugung, Volumenverteilung). Die Mittel können jedoch bis zu 6 Gew.-% Teilchen mit einer Größe im Bereich von 0,2 bis 2 mm enthalten, ohne daß die Stabilität der Mittel beeinträchtigt wird. Vorzugsweise enthalten die Mittel max. 5 Gew.-% an Granulaten dieser Größenordnung.The liquid detergents according to the invention can contain other solids in addition to those mentioned contained in dispersed form. The ratio of fixed parts: liquid parts do not exceed the value 40:60. The dispersed solids preferably have an average grain size of 1 to 10 µm and especially 1 to 5 µm (measurement method: Coulter counter or Fraunhofer diffraction, volume distribution). However, the funds can be up to to 6 wt .-% contain particles with a size in the range of 0.2 to 2 mm, without the Stability of funds is compromised. The agents preferably contain max. 5% by weight Granules of this size.

    Falls gewünscht, können die Mittel weitere übliche Bestandteile wie anorganische und organische Gerüstsubstanzen, Carbonate, Silikate, Hydroxide, Schauminhibitoren, optische Aufheller, Enzyme sowie Farb- und Duftstoffe enthalten.If desired, the agents can include other conventional components such as inorganic and organic Builders, carbonates, silicates, hydroxides, foam inhibitors, optical brighteners, Contain enzymes as well as colors and fragrances.

    Als organische und anorganische Gerüstsubstanzen eignen sich neutral oder insbesondere alkalisch reagierende Salze, die Calciumionen auszufallen oder komplex zu binden vermögen. Geeignete und insbesondere ökologisch unbedenkliche Buildersubstanzen, wie feinkristalline, synthetische wasserhaltige Zeolithe vom Typ NaA, die ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g (gemäß den Angaben in DE 24 12 837) aufweisen, finden eine bevorzugte Verwendung. Ihre mittlere Teilchengröße (Meßmethode: Coulter Counter, Volumenverteilung) liegt üblichereweise im Bereich von 1 bis 10 µm und vorzugsweise im Bereich von 1 bis 5 µm. In nichtwäßrigen Systemen werden bevorzugt Schichtsilikate eingesetzt. Zeolith und die Schichtsilikate können in einer Menge bis zu 20 Gew.-%,. im Mittel enthalten sein. Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, und Nitrilotriacetat (NTA), sofem ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist. Analog hierzu können auch polymere Carboxylate und deren Salze eingesetzt werden. Hierzu gehören beispielsweise die Salze homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure und auch Polyvinylpyrrolidon und Urethane. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1 000 und 100 000, die der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol® 940 und 941 erhältlichen Polymere. Die quervemetzten Polyacrylate werden in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt. Diese Gerüstsubstanzen können in Mengen bis zu 5 Gew.-% eingesetzt werden.Neutral or in particular are suitable as organic and inorganic builders alkaline reacting salts that can precipitate calcium ions or bind them in a complex manner. Suitable and in particular ecologically harmless builder substances, such as fine crystalline synthetic water-containing zeolites of the type NaA, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) are preferred Use. Your average particle size (measurement method: Coulter Counter, volume distribution) is usually in the range from 1 to 10 μm and preferably in the range from 1 up to 5 µm. Layered silicates are preferably used in non-aqueous systems. Zeolite and the layered silicates can be used in an amount of up to 20% by weight. to be included in the average. Usable organic builders are, for example, the preferred ones in the form of their sodium salts used polycarboxylic acids, such as citric acid, and nitrilotriacetate (NTA), so far such use is not objectionable for ecological reasons. Analogously to this polymeric carboxylates and their salts are also used. These include, for example the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular Copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% Maleic acid and also polyvinyl pyrrolidone and urethanes. The relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. Especially water-soluble polyacrylates are also suitable, for example with about 1% of a polyallyl ether of sucrose are cross-linked and have a relative molecular weight above own a million. Examples of this are those under the name Carbopol® 940 and 941 available polymers. The crosslinked polyacrylates are used in amounts not exceeding 1% by weight, preferably used in amounts of 0.2 to 0.7 wt .-%. These frameworks can can be used in amounts of up to 5% by weight.

    Zusätzlich können die erfindungsgemäßen Mittel weitere nichttensidartige Schauminhibitoren enthalten, obwohl diese aber in den erfindungsgemäßen Mitteln nicht erforderlich sind, um das Schaumverhalten zu verbessem. Geeignete Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Nikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.In addition, the agents according to the invention can contain other non-surfactant-like foam inhibitors included, although these are not required in the agents according to the invention in order to To improve foam behavior. Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica and Paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. With Mixtures of different foam inhibitors can also advantageously be used, e.g. such made of silicone oil, paraffin oil or wax. The foam inhibitors are preferably attached to one granular, water-soluble or dispersible carrier substance bound.

    Die Flüssigwaschmittel enthalten als optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze, die sich gut in die Dispersion einarbeiten lassen. Der maximale Gehalt an Aufhellern in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.The liquid detergents contain, for example, derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts, which work well into the dispersion to let. The maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.

    Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 bis 1 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein.Enzymes come from the class of proteases, lipases, amylases or their Mixtures in question. Their proportion can be 0.2 to 1% by weight. The enzymes can on carriers adsorbed and / or embedded in coating substances.

    Um Spuren von Schwermetallen zu binden, können die Salze von Polyphosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und Diethylentriaminpentamethylenphosphonsäure (DTPMP) eingesetzt werden. To bind traces of heavy metals, the salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be used.

    In einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel 3 Gew.-% bis 30 Gew.-% nichtionische Tenside, 3 Gew.-% bis 15 Gew.-% anionische Tenside bis zu 2 Gew.-% Verdicker, bis zu 15 Gew.-% Gerüstsubstanzen, 0,05 Gew.-% bis 0,2 Gew.-% optische Aufheller und 0,3 Gew.-% bis 1,5 Gew.-% Enzyme.In a preferred embodiment, the agent according to the invention contains 3% by weight to 30% % By weight nonionic surfactants, 3% by weight to 15% by weight anionic surfactants up to 2% by weight Thickeners, up to 15% by weight of framework substances, 0.05% by weight to 0.2% by weight of optical brighteners and 0.3 wt% to 1.5 wt% enzymes.

    Die Flüssigwaschmittel können beispielsweise durch einfaches Vermischen oder durch Naßvermahlung der Mischung aus Alkylpolyglycosiden, Fettsäurealkylesteralkoxylate und Schwefelsäuremonoestersalze erhalten werden. Dazu werden weitere Tenside, Lösungsmittel, falls erwünscht Verdickungsmittel, und ggf. ein Entschäumer in einen Reaktor gegeben, der mit einem Rührsystem versehen ist, und miteinander vermischt. Im Anschluß daran können weitere Bestandteile des Mittels einzeln oder im Gemisch hinzudosiert werden. Daraufhin erfolgt die Naßvermahlung der Dispersion bei Temperaturen bis maximal 70°C, vorzugsweise aber bei Temperaturen bis 32°C und insbesondere bei Raumtemperatur. Die Dauer der Vermahlung beträgt maximal 30 Minuten. Vorzugsweise wird die Vermahlung in wesentlich kürzeren Zeiten, beispielsweise zwischen 3 und 10 Minuten durchgeführt. Für diesen Zweck eignen sich insbesondere hochtourige und feinvermahlende Kolloid- und Ringspaltkugelmühlen. Gegebenenfalls vorhandenes Triacetin wird bevorzugt nach der Vermahlung zur Dispersion hinzugegeben.The liquid detergents can be mixed, for example, by simple mixing or by wet grinding the mixture of alkyl polyglycosides, fatty acid alkyl ester alkoxylates and sulfuric acid monoester salts be preserved. For this purpose, further surfactants, solvents, if Desired thickener, and optionally a defoamer placed in a reactor with is provided with a stirring system and mixed together. Following this, others can Components of the agent are added individually or in a mixture. Then the Wet grinding of the dispersion at temperatures up to a maximum of 70 ° C, but preferably at Temperatures up to 32 ° C and especially at room temperature. The duration of the grinding is a maximum of 30 minutes. The grinding is preferably carried out in significantly shorter times, for example between 3 and 10 minutes. Are particularly suitable for this purpose high-speed and finely ground colloid and annular gap ball mills. Possibly Triacetin present is preferably added to the dispersion after grinding.

    Der Stockpunkt der Mittel liegt vorzugsweise unterhalb von 10°C und insbesondere unterhalb von 6°C. Der pH-Wert der Mittel liegt zwischen 6 und 10 und vorzugsweise zwischen 7,5 und 9,5. Die Mittel waren mindestens 3 Monate lang sowohl bei Raumtemperatur als auch bei 40°C stabil. Bei schon länger gelagerten Ansätzen wurde auch nach 12 Monaten kein Absetzen beobachtet.The pour point of the agents is preferably below 10 ° C. and in particular below of 6 ° C. The pH of the compositions is between 6 and 10 and preferably between 7.5 and 9.5. The agents were at room temperature as well as at 40 ° C for at least 3 months stable. In the case of approaches that had been stored for a long time, there was no weaning even after 12 months observed.

    Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von Flüssigwaschmitteln, welche 0,1 bis 40 Gew.-% eines Alkylpolyglycosids mit der Formel I R1-O-[Z]x worin R1 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 8 bis 18 C-Atomen, Z einen Zuckerrest, vorzugsweise einen Glucose- oder Xylose-Rest und x eine ganze Zahl von 1 bis 10 darstellt,
    5 Gew.-% bis 20 Gew.-% mindestens eines Fettsäurealkylesteralkoxylats mit der Formel II, III oder IV R2-CO2-(A0)y-R3 R3-CO2-(AO)y-R2

    Figure 00110001
    worin

    R2
    für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 7 bis 17 C-Atomen,
    R3
    für eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 C-Atomen steht,
    R4, R5 und R6
    gleich oder verschieden sein können und für Wasserstoff oder
    Figure 00110002
    worin R7 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen sein kann, mit der Maßgabe, daß R4, R5 und R6 nicht gleichzeitig Wasserstoff sind, AO für eine C2-C4-Alkylenoxydeinheit steht, y für eine Zahl von 1 bis 30, vorzugweise 5 bis 25, insbesondere 9 bis 18, und n, o und p gleich oder verschieden seien können und für eine Zahl von 1 bis 60, vor zugsweise 1 bis 30, insbesondere 3 bis 12, stehen, und mehr als 2 Gew.-% bis 20 Gew.-% mindestens eines Salzes von Schwefelsäuremonoestern der C6- bis C18-Fettalkohole zum Waschen von Textilien.
    Another object of the present invention is the use of liquid detergents which contain 0.1 to 40% by weight of an alkyl polyglycoside with the formula I. R 1 -O- [Z] x in which R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or xylose residue and x is an integer from 1 to 10,
    5% by weight to 20% by weight of at least one fatty acid alkyl ester alkoxylate with the formula II, III or IV R 2 -CO 2 - (A0) y -R 3 R 3 -CO 2 - (AO) y -R 2
    Figure 00110001
    wherein
    R 2
    for a branched or straight-chain, saturated or unsaturated alkyl group with 7 to 17 carbon atoms,
    R 3
    represents a straight-chain or branched-chain alkyl group having 1 to 6 C atoms,
    R 4 , R 5 and R 6
    can be the same or different and for hydrogen or
    Figure 00110002
    wherein R 7 can be a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, with the proviso that R 4 , R 5 and R 6 are not simultaneously hydrogen, AO for a C 2 -C 4 alkylene oxide unit is, y is a number from 1 to 30, preferably 5 to 25, in particular 9 to 18, and n, o and p may be the same or different and for a number from 1 to 60, preferably 1 to 30, in particular 3 to 12, stand, and more than 2 wt .-% to 20 wt .-% of at least one salt of sulfuric acid monoesters of C 6 to C 18 fatty alcohols for washing textiles.

    Für die erfindungsgemäße Verwendung ist es nicht erforderlich, daß die erfindungsgemäß eingesetzten Mittel optische Aufheller enthalten. Obwohl die Verwendung Aufheller-haltiger Mittel bevorzugt ist, können im erfindungsgemäßen Verfahren auch Mittel eingesetzt werden, die frei von optischen Aufheller sind. Bis auf diese Ausnahme sind bevorzugte Verwendungsformen solche, in denen die oben als bevorzugt bezeichneten Mittel eingesetzt werden. Bevorzugte Verwendungen sind also solche, in denen im Alkylpolyglycosid mit der Formel I R1 eine Alkylgruppe mit 8 bis 14 Kohlenstoffatomen darstellt und im Fettsäurealkylesteralkoxylat mit der Formel II oder III AO für eine Ethylenoxid-Einheit und R3 für eine Methylgruppe steht oder bei denen weitere nichtionische Tenside ausgewählt aus der Gruppe der C6-C18-Alkylpolyglykolether, Zuckerester, C6-C18-Fettsäurepolyglykolether, Sorbitanfettsäureester, C6-C18-Fettsäurepartial-glyceride sowie deren Mischungen in einer Menge von bis zu 60 Gew.-%, bezogen auf das gesamte Mittel, enthalten sind, wobei in besonders bevorzugten Verwendungen das nichtionische Tensid ausgewählt ist aus der Gruppe der C6-C18-Alkylpolyglykolether.For the use according to the invention it is not necessary that the agents used according to the invention contain optical brighteners. Although the use of brightener-containing agents is preferred, agents which are free from optical brighteners can also be used in the process according to the invention. Except for this exception, preferred forms of use are those in which the agents designated above as preferred are used. Preferred uses are therefore those in which the alkyl polyglycoside with the formula IR 1 represents an alkyl group with 8 to 14 carbon atoms and in the fatty acid alkyl ester alkoxylate with the formula II or III AO represents an ethylene oxide unit and R 3 represents a methyl group or in which other nonionic groups Surfactants selected from the group of C 6 -C 18 alkyl polyglycol ethers, sugar esters, C 6 -C 18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides and mixtures thereof in an amount of up to 60% by weight, based on the total agent, are included, the nonionic surfactant being selected from the group of the C 6 -C 18 -alkyl polyglycol ethers in particularly preferred uses.

    In weiteren bevorzugten Verwendungen enthält das einzusetzende Mittel weitere anionische Tenside ausgewählt aus der Gruppe C6-C18-Alkylbenzolsulfonate, C6-C18-Alkansulfonate, C6-C18-Alkylpolyglycolethersullate, α-Olefinsulfonate, C6-C18-Alkylpolyglycolethersulfonate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Seifen, Amidseifen, C6-C18-Fettsäureamid-Ethersulfate, C6-C18-Alkylcarboxylate, Fettsäureisethionate, N-C6-C18-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride, C6-C18-Alkyloligoglucosidsulfate, C6-C18-Alkylphosphate sowie deren Mischungen in einer Gesamtmenge von bis zu 40 Gew.-%, bezogen auf das gesamte Mittel, enthalten sind, bezogen auf das gesamte Mittel. Hierbei ist es wiederum bevorzugt, daß das Aniontensid ausgewählt ist aus der Gruppe der C6-C18-Alkylpolyglykolethersulfate, der Seifen und der C6-C18-Alkansulfonate sowie deren Mischungen.In further preferred uses, the agent to be used contains further anionic surfactants selected from the group C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl polyglycol ether sulfates, α-olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates , glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 18 fatty acid amide ether sulfates, C 6 -C 18 alkyl carboxylates, fatty acid isethionates, NC 6 -C 18 acyl sarcosinates, NC 6 - C 18 acyl taurides, C 6 -C 18 alkyl oligoglucoside sulfates, C 6 -C 18 alkyl phosphates and mixtures thereof are present in a total amount of up to 40% by weight, based on the total agent, based on the total Medium. Here again it is preferred that the anionic surfactant is selected from the group of the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and mixtures thereof.

    In besonders bevorzugten Verwendungen enthält das eingesetzte Mittel 3 Gew.-% bis 30 Gew.-% nichtionische Tenside, 2 Gew.-% bis 15 Gew.-% anionische Tenside bis zu 2 Gew.-% Verdicker, bis zu 15 Gew.-% Gerüstsubstanzen, 0,05 Gew.-% bis 0,2 Gew.-% optische Aufheller und 0,3 Gew.-% bis 1,5 Gew.-% Enzyme. In particularly preferred uses, the agent used contains 3% by weight to 30% % By weight nonionic surfactants, 2% by weight to 15% by weight anionic surfactants up to 2% by weight Thickeners, up to 15% by weight of framework substances, 0.05% by weight to 0.2% by weight of optical Brightener and 0.3 wt% to 1.5 wt% enzymes.

    BeispieleExamples

    Die schaumdämpfende Wirkung von Fettsäurealkylesteralkoxylaten auf starkschäumende Tenside wurde in den folgenden Beispielen untersucht. Die Rezepturen der untersuchten Flüssigwaschmittel sind in den Tabellen 1 und 2 aufgeführt. Die angegebenen Mengenangaben bedeuten Gew.-%, bezogen auf das Mittel.The foam-suppressing effect of fatty acid alkyl ester alkoxylates on high-foaming Surfactants were examined in the following examples. The recipes of the examined Liquid detergents are listed in Tables 1 and 2. The specified quantities mean% by weight, based on the average.

    Es wurden folgende Fettsäurealkylesteralkoxylate mit der Formel II eingesetzt:

    A
    C12-Fettsäuremethylester x 15 Ethylenoxideinheiten
    B
    C12/14-Fettsäuremethylester x 6 Ethylenoxideinheiten
    C
    C12/14-Fettsäure-n-Butylester x 6 Ethylenoxideinheiten
    D
    C12/18-Fettsäuremethylester x 3 Ethylenoxideinheiten
    E
    C12/18-Fettsäuremethylester x 5 Ethylenoxideinheiten
    F
    C12/18-Fettsäure-n-Butylester x 5 Ethylenoxideinheiten
    G
    C12/18-Fettsäuremethylester x 7 Ethylenoxideinheiten
    H
    C16/18-Fettsäuremethylester x 3 Ethylenoxideinheiten
    I
    C16/18-Fettsäuremethylester x 4 Ethylenoxideinheiten
    K
    C16/18-Fettsäuremethylester x 5 Ethylenoxideinheiten
    L
    C16/18-Fettsäuremethylester x 7 Ethylenoxideinheiten
    Figure 00140001
    Figure 00150001
    The following fatty acid alkyl ester alkoxylates with the formula II were used:
    A
    C 12 fatty acid methyl ester x 15 ethylene oxide units
    B
    C 12/14 fatty acid methyl ester x 6 ethylene oxide units
    C.
    C 12/14 fatty acid n-butyl ester x 6 ethylene oxide units
    D
    C 12/18 fatty acid methyl ester x 3 ethylene oxide units
    E
    C 12/18 fatty acid methyl ester x 5 ethylene oxide units
    F
    C 12/18 fatty acid n-butyl ester x 5 ethylene oxide units
    G
    C 12/18 fatty acid methyl ester x 7 ethylene oxide units
    H
    C 16/18 fatty acid methyl ester x 3 ethylene oxide units
    I.
    C 16/18 fatty acid methyl ester x 4 ethylene oxide units
    K
    C 16/18 fatty acid methyl ester x 5 ethylene oxide units
    L
    C 16/18 fatty acid methyl ester x 7 ethylene oxide units
    Figure 00140001
    Figure 00150001

    Die Versuchsergebnisse der Schaumprüfung sind in den Tabellen 3 bis 11 wiedergegeben. Die Schaumprüfung wurde bei einer Temperatur von 60°C und einer Wasserhärte von 16 ± 2°d durchgeführt. Das Mittel wurde in einer Konzentration von 45,9 g/l Wasser dosiert. Die Menge des gebildeten Schaumes wurde mit Noten von 0 bis 6 bewertet, wobei die Noten wie folgt vergeben wurden:

    0
    kein Schaum
    1
    Schaum im Bullauge der Waschmaschine gerade sichtbar
    3
    Bullauge der Waschmaschine bis zur Hälfte mit Schaum bedeckt
    5
    Bullauge der Waschmaschine nahezu vollständig mit Schaum bedeckt
    6
    Überschäumen, d.h. Austreten des Schaums aus der Waschmaschine
    Rezeptur Testzeit in Minuten 2 5 7 10 1A 0,6 0,7 0,8 0,8 1B 0,2 0,4 0,5 0,5 1C 0 0 0 0 1D 0 0 0 0 1E 0 0 0 0 1F 0 0 0 0 1G 0 0 0 0,5 1H 0 0 0 0 1I 0 0 0 0 1K 0 0 0 0 1L 0 0 0 0 10 3,1 4,6 5,0 5,2 Rezeptur Testzeit in Minuten 2 5 7 10 2A 0,8 1 1 1,2 2B 0,5 0,5 0,5 0,7 2C 0 0 0,2 0,5 2D 0 0 0 0 2E 0 0 0,2 0,2 2F 0 0 0 0 2G 0 0 0 0,5 2H 0 0 0 0 2I 0 0 0 0,2 2K 0 0 0 0 2L 0 0 0 0 11 2,5 3,5 4,2 4,8 Rezeptur Testzeit in Minuten 2 5 7 10 3A 1 1 1,5 1,5 3B 0,5 0,5 0,5 0,5 3C 0 0 0,5 0,5 3D 0 0 0 0 3E 0 0 0,2 0,2 3F 0 0 0 0 3G 0 0,2 0,5 0,5 3H 0 0 0 0 3I 0 0 0 0 3K 0 0 0 0 3L 0 0 0 0 12 2 3,2 3,8 4,0 Rezeptur Testzeit in Minuten 2 5 7 10 4A 3,5 4,3 5 5,5 4B 3,5 3,7 4,3 4,8 4C 3,5 4 4,5 4,8 4D 0,5 0,5 0,5 0,5 4E 1 1 1 1 4F 1 1 1 1 4G 3 3,7 4,2 4,7 4H 1 1 1 1 4i 1 1 1 1 4K 1 1,3 1,3 1,3 4L 1,3 1,5 1,7 1,8 13 3,7 4,8 5,2 5,7 Rezeptur Testzeit in Minuten 2 5 7 10 5A 2,5 3,8 3,8 5 5B 2,5 2,8 3,2 4,5 5C 1,5 1,8 2,3 2,7 5D 0,5 0,5 0,5 0,5 5E 1 1 1 1 5F 1 1 1 1 5G 2 2,7 3,2 3,5 5H 1,5 1,5 1,7 1,8 5I 1,5 1,5 1,7 1,8 5K 1 1,3 1,3 1,5 5L 1,5 2 2,5 2,8 14 2,7 3,5 4,8 5,5 Rezeptur Testzeit in Minuten 2 5 7 10 6A 2,5 3 4,5 5 6B 2 2,3 3,5 3,8 6c 1,2 1,5 1,7 1,9 6D 0,5 0,5 0,5 0,5 6E 1 1 1 1 6F 1 1 1 1 6G 2 3,3 3,7 4,2 6H 0,7 1,2 1,5 1,5 6I 1,5 1,5 1,5 1,5 6K 1,5 1,5 1,5 1,5 6L 1,5 2,2 2,5 3 15 2,3 4,0 5,0 5,5 Rezeptur Testzeit in Minuten 2 5 7 10 7A 2 4,7 5,0 5,0 78 2 2,2 2,7 2,8 7C 1 1,2 1,5 1,5 7D 1 1 1 1 7E 1 1 1 1 7F 1 1 1 1 7G 2 3,2 3,7 4,2 7H 1 1 1 1 7I 1 1 1 1 7K 1 1 1 1 7L 1 1 1 1 16 2,8 4,8 5,5 5,5 Rezeptur Testzeit in Minuten 2 7 10 8A 2 2,7 3,7 4,3 8B 1 1,3 1,3 1,2 8C 1,5 1,7 1,8 2 8D 1 1 1 1 8E 1 1 1 1 8F 1 1 1 1 8G 1,5 2,8 3,2 4,7 8H 1 1,2 1,4 1,8 8I 1 1,2 1,5 1,8 8K 1,2 1,2 1,6 1,7 8L 1,2 1,4 1,6 1,8 17 2,7 3,5 4,8 5,5 Rezeptur Testzeit in Minuten 2 5 7 10 9A 1,3 1,8 2,8 4,3 9B 0,3 1 1 1 9c 1 1 1 1 90 1 1 1 1 9E 1 1 1 1 9F 1 1 1 1 9G 1 1,2 1,5 1,7 9H 1 1 1 1 9i 1 1 1 1 9K 1 1 1 1 9L 1 1 1 1 18 1,8 2,3 3,8 4,8 The test results of the foam test are shown in Tables 3 to 11. The foam test was carried out at a temperature of 60 ° C and a water hardness of 16 ± 2 ° d. The agent was dosed in a concentration of 45.9 g / l water. The amount of foam formed was rated with grades from 0 to 6, the grades being assigned as follows:
    0
    no foam
    1
    Foam just visible in the washing machine's porthole
    3rd
    The washing machine's porthole is half covered with foam
    5
    The washing machine's porthole is almost completely covered with foam
    6
    Exuberance, ie the foam comes out of the washing machine
    Recipe Test time in minutes 2nd 5 7 10th 1A 0.6 0.7 0.8 0.8 1B 0.2 0.4 0.5 0.5 1C 0 0 0 0 1D 0 0 0 0 1E 0 0 0 0 1F 0 0 0 0 1G 0 0 0 0.5 1H 0 0 0 0 1I 0 0 0 0 1K 0 0 0 0 1L 0 0 0 0 10th 3.1 4.6 5.0 5.2 Recipe Test time in minutes 2nd 5 7 10th 2A 0.8 1 1 1.2 2 B 0.5 0.5 0.5 0.7 2C 0 0 0.2 0.5 2D 0 0 0 0 2E 0 0 0.2 0.2 2F 0 0 0 0 2G 0 0 0 0.5 2H 0 0 0 0 2I 0 0 0 0.2 2K 0 0 0 0 2L 0 0 0 0 11 2.5 3.5 4.2 4.8 Recipe Test time in minutes 2nd 5 7 10th 3A 1 1 1.5 1.5 3B 0.5 0.5 0.5 0.5 3C 0 0 0.5 0.5 3D 0 0 0 0 3E 0 0 0.2 0.2 3F 0 0 0 0 3G 0 0.2 0.5 0.5 3H 0 0 0 0 3I 0 0 0 0 3K 0 0 0 0 3L 0 0 0 0 12th 2nd 3.2 3.8 4.0 Recipe Test time in minutes 2nd 5 7 10th 4A 3.5 4.3 5 5.5 4B 3.5 3.7 4.3 4.8 4C 3.5 4th 4.5 4.8 4D 0.5 0.5 0.5 0.5 4E 1 1 1 1 4F 1 1 1 1 4G 3rd 3.7 4.2 4.7 4H 1 1 1 1 4i 1 1 1 1 4K 1 1.3 1.3 1.3 4L 1.3 1.5 1.7 1.8 13 3.7 4.8 5.2 5.7 Recipe Test time in minutes 2nd 5 7 10th 5A 2.5 3.8 3.8 5 5B 2.5 2.8 3.2 4.5 5C 1.5 1.8 2.3 2.7 5D 0.5 0.5 0.5 0.5 5E 1 1 1 1 5F 1 1 1 1 5G 2nd 2.7 3.2 3.5 5H 1.5 1.5 1.7 1.8 5I 1.5 1.5 1.7 1.8 5K 1 1.3 1.3 1.5 5L 1.5 2nd 2.5 2.8 14 2.7 3.5 4.8 5.5 Recipe Test time in minutes 2nd 5 7 10th 6A 2.5 3rd 4.5 5 6B 2nd 2.3 3.5 3.8 6c 1.2 1.5 1.7 1.9 6D 0.5 0.5 0.5 0.5 6E 1 1 1 1 6F 1 1 1 1 6G 2nd 3.3 3.7 4.2 6H 0.7 1.2 1.5 1.5 6I 1.5 1.5 1.5 1.5 6K 1.5 1.5 1.5 1.5 6L 1.5 2.2 2.5 3rd 15 2.3 4.0 5.0 5.5 Recipe Test time in minutes 2nd 5 7 10th 7A 2nd 4.7 5.0 5.0 78 2nd 2.2 2.7 2.8 7C 1 1.2 1.5 1.5 7D 1 1 1 1 7E 1 1 1 1 7F 1 1 1 1 7G 2nd 3.2 3.7 4.2 7H 1 1 1 1 7I 1 1 1 1 7K 1 1 1 1 7L 1 1 1 1 16 2.8 4.8 5.5 5.5 Recipe Test time in minutes 2nd 7 10th 8A 2nd 2.7 3.7 4.3 8B 1 1.3 1.3 1.2 8C 1.5 1.7 1.8 2nd 8D 1 1 1 1 8E 1 1 1 1 8F 1 1 1 1 8G 1.5 2.8 3.2 4.7 8H 1 1.2 1.4 1.8 8I 1 1.2 1.5 1.8 8K 1.2 1.2 1.6 1.7 8L 1.2 1.4 1.6 1.8 17th 2.7 3.5 4.8 5.5 Recipe Test time in minutes 2nd 5 7 10th 9A 1.3 1.8 2.8 4.3 9B 0.3 1 1 1 9c 1 1 1 1 90 1 1 1 1 9E 1 1 1 1 9F 1 1 1 1 9G 1 1.2 1.5 1.7 9H 1 1 1 1 9i 1 1 1 1 9K 1 1 1 1 9L 1 1 1 1 18th 1.8 2.3 3.8 4.8

    Aus den Tabellen 3 bis 7 wird deutlich, daß die Mittel gemäß der Erfindung eine wesentlich geringere Schaumbildung zeigen als die Mittel der Vergleichsbeispiele.From Tables 3 to 7 it is clear that the means according to the invention are essential show less foaming than the agents of the comparative examples.

    Claims (14)

    1. A liquid detergent containing
      0.1% by weight to 40% by weight of an alkyl polyglycoside corresponding to formula I: R1-O-[Z]x in which R1 is a branched or linear, saturated or unsaturated alkyl group containing 8 to 18 carbon atoms, Z is a sugar unit, preferably a glucose or xylose unit, and x is an integer of 1 to 10,
      5% by weight to 20% by weight of at least one fatty acid alkyl ester alkoxylate corresponding to general formula II, III or IV: R2 -CO2-(AO)y-R3 R3-CO2-(AO)y-R2
      Figure 00270001
      in which
      R2
      is a branched or linear, saturated or unsaturated alkyl group containing 7 to 17 carbon atoms,
      R3
      is a linear or branched alkyl group containing 1 to 6 carbon atoms,
      R4 ,R5 and R6,
      which may be the same or different, represent hydrogen or
      Figure 00280001
      where R7 is a branched or linear, saturated or unsatrated alkyl group containing 5 to 21 carbon atoms, with the proviso that R4, R5 and R6 cannot all be hydrogen,
      AO
      is a C2-4 alkylene oxide unit, y is a number of 1 to 30, preferably 5 to 25 and more preferably 9 to 18 and n, o and p which may be the same or different stand for a number of 1 to 60, preferably 1 to 30 and more preferably 3 to 12
      and more than 2% by weight to 20% by weight of at least one salt of sulfuric acid monoesters of C6-18 fatty alcohols and 0.02 to 0.5% by weight of optical brighteners.
    2. A detergent as claimed in claim 1, characterized in that, in the alkyl polyglycoside corresponding to formula I, R1 is an alkyl group containing 8 to 14 carbon atoms and, in the fatty acid alkyl ester alkoxylate corresponding to formula II or III, AO stands for an ethylene oxide unit and R3 for a methyl group.
    3. A detergent as claimed in claim 1, characterized in that other nonionic surfactants selected from the group of C6-18 alkyl polyglycol ethers, sugar esters, C6-18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C6-18 fatty acid partial glycerides and mixtures thereof are present in a quantity of up to 60% by weight, based on the detergent as a whole.
    4. A detergent as claimed in claim 3, characterized in that the nonionic surfactant is selected from the group of C6-18 alkyl polyglycol ethers.
    5. A detergent as claimed in any of claims 1 to 4, characterized in that other anionic surfactants selected from the group of C6-18 alkyl benzenesulfonates, C6-18 alkane sulfonates, C6-18 alkyl polyglycol ether sulfates, α-olefin sulfonates, C6-18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C6-18 fatty acid amide ether sulfates, C6-18 alkyl carboxylates, fatty acid isethionates, N-C6-18-acyl sarcosinates, N-C6-18-acyl taurides, C6-18 alkyl oligoglucoside sulfates, C6-18 alkyl phosphates and mixtures thereof are present in a total quantity of up to 40% by weight, based on the detergent as a whole.
    6. A detergent as claimed in claim 5, characterized in that the anionic surfactant is selected from the group of C6-18 alkyl polyglycol ether sulfates, soaps and C6-18 alkane sulfonates and mixtures thereof.
    7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains 3% by weight to 30% by weight of nonionic surfactants, 2% by weight to 15% by weight of anionic surfactants, up to 2% by weight of thickeners, up to 15% by weight of builders, 0.05% by weight to 0.2% by weight of optical brighteners and 0.3% by weight to 1.5% by weight of enzymes.
    8. The use of liquid detergents containing
      0.1% by weight to 40% by weight of an alkyl polyglycoside corresponding to formula I: R1-O-[Z]x in which R1 is a branched or linear, saturated or unsaturated alkyl group containing 8 to 18 carbon atoms, Z is a sugar unit, preferably a glucose or xylose unit, and x is an integer of 1 to 10,
      5% by weight to 20% by weight of at least one fatty acid alkyl ester alkoxylate corresponding to general formula II, III or IV: R2-CO2-(AO)y-R3 R3-CO2-(AO)y-R2
      Figure 00300001
      in which
      R2
      is a branched or linear, saturated or unsaturated alkyl group containing 7 to 17 carbon atoms,
      R3
      is a linear or branched alkyl group containing 1 to 6 carbon atoms,
      R4 ,R5 and R6,
      which may be the same or different, represent hydrogen or
      Figure 00300002
      where R7 is a branched or linear, saturated or unsatrated alkyl group containing 5 to 21 carbon atoms, with the proviso that R4, R5 and R6 cannot all be hydrogen,
      AO
      is a C2-4 alkylene oxide unit, y is a number of 1 to 30, preferably 5 to 25 and more preferably 9 to 18 and n, o and p which may be the same or different stand for a number of 1 to 60, preferably 1 to 30 and more preferably 3 to 12
      and more than 2% by weight to 20% by weight of at least one salt of sulfuric acid monoesters of C6-18 fatty alcohols,
      for washing textiles.
    9. The use claimed in claim 8, characterized in that, in the alkyl polyglycoside corresponding to formula I, R1 is an alkyl group containing 8 to 14 carbon atoms and, in the fatty acid alkyl ester alkoxylate corresponding to formula II or III, AO stands for an ethylene oxide unit and R3 for a methyl group.
    10. The use claimed in claim 8, characterized in that other nonionic surfactants selected from the group of C6-18 alkyl polyglycol ethers, sugar esters, C6-18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C6-18 fatty acid partial glycerides and mixtures thereof are present in a quantity of up to 60% by weight, based on the detergent as a whole.
    11. The use claimed in claim 10, characterized in that the nonionic surfactant is selected from the group of C6-18 alkyl polyglycol ethers.
    12. The use claimed in any of claims 8 to 11, characterized in that other anionic surfactants selected from the group of C6-18 alkyl benzenesulfonates, C6-18 alkane sulfonates, C6-18 alkyl polyglycol ether sulfates, α-olefin sulfonates, C6-18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C6-18 fatty acid amide ether sulfates, C6-18 alkyl carboxylates, fatty acid isethionates, N-C6-18-acyl sarcosinates, N-C6-18-acyl taurides, C6-18 alkyl oligoglucoside sulfates, C6-18 alkyl phosphates and mixtures thereof are present in a total quantity of up to 40% by weight, based on the detergent as a whole.
    13. The use claimed in claim 12, characterized in that the anionic surfactant is selected from the group of C6-18 alkyl polyglycol ether sulfates, soaps and C6-18 alkane sulfonates and mixtures thereof.
    14. The use claimed in any of claims 8 to 13, characterized in that the detergent used contains 3% by weight to 30% by weight of nonionic surfactants, 2% by weight to 15% by weight of anionic surfactants, up to 2% by weight of thickeners, up to 15% by weight of builders, 0.05% by weight to 0.2% by weight of optical brighteners and 0.3% by weight to 1.5% by weight of enzymes.
    EP96901298A 1995-01-27 1996-01-18 Liquid detergent Expired - Lifetime EP0805846B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19502454A DE19502454A1 (en) 1995-01-27 1995-01-27 Liquid detergent
    DE19502454 1995-01-27
    PCT/EP1996/000198 WO1996023049A1 (en) 1995-01-27 1996-01-18 Liquid detergent

    Publications (2)

    Publication Number Publication Date
    EP0805846A1 EP0805846A1 (en) 1997-11-12
    EP0805846B1 true EP0805846B1 (en) 1999-07-14

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    DE (2) DE19502454A1 (en)
    ES (1) ES2135204T3 (en)
    WO (1) WO1996023049A1 (en)

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    DE19853110A1 (en) 1998-11-18 2000-05-25 Cognis Deutschland Gmbh Gel-shaped detergent for flush toilets
    DE60023126T2 (en) * 1999-04-30 2006-07-06 Colgate-Palmolive Co. LIQUID CLEANING COMPOSITIONS USING A METHYLETHOXYLATED ESTER
    DE19937293A1 (en) * 1999-08-06 2001-02-15 Cognis Deutschland Gmbh Use of alkoxylated carboxylic acid esters as foam boosters
    DE19939804A1 (en) * 1999-08-21 2001-02-22 Cognis Deutschland Gmbh Foam controlled solid detergent contains a non-ionic surfactant(s) and an alkyl and/or alkenyl oligoglycoside
    US7098175B2 (en) * 2004-06-08 2006-08-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Aqueous detergent composition containing ethoxylated fatty acid di-ester
    US7205268B2 (en) 2005-02-04 2007-04-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Low-foaming liquid laundry detergent
    US7291582B2 (en) 2005-09-20 2007-11-06 Conopco, Inc., D/B/A Unilever Liquid laundry detergent with an alkoxylated ester surfactant
    US20070111914A1 (en) * 2005-11-16 2007-05-17 Conopco, Inc., D/B/A Unilever, A Corporation Of New York Environmentally friendly laundry method and kit
    DE602007010280D1 (en) 2006-06-08 2010-12-16 Unilever Nv LIQUID DETERGENT WITH ESTERAL COXYLATE AS A TENSID AND UREA
    CZ301476B6 (en) * 2007-06-15 2010-03-17 Vysoká škola chemicko-technologická v Praze Detergent composition exhibiting high washing efficiency and low formation of incrusting solids and containing only wetting agents produced from renewable raw materials
    CN116103096A (en) 2014-06-30 2023-05-12 宝洁公司 Laundry detergent composition
    WO2016023145A1 (en) 2014-08-11 2016-02-18 The Procter & Gamble Company Laundry detergent
    WO2019023016A1 (en) * 2017-07-28 2019-01-31 Croda, Inc. Cleaning formulation comprising a solvent additive

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    US4343726A (en) * 1979-05-07 1982-08-10 Sherex Chemical Company, Inc. Low irritating high viscosity detergent composition
    JPS58217598A (en) * 1982-06-10 1983-12-17 日本油脂株式会社 Detergent composition
    EP0105556A1 (en) * 1982-09-30 1984-04-18 THE PROCTER & GAMBLE COMPANY Liquid detergent composition containing nonionic and ionic surfactants
    ATE114707T1 (en) * 1990-08-22 1994-12-15 Henkel Kgaa LIQUID DETERGENT WITH INCREASED VISCOSITY.
    DE4227046A1 (en) * 1991-08-15 1993-02-18 Lion Corp Detergent compsn. contg. fatty acid ester of polyoxyalkylene alkyl ether - prepd. from fatty acid alkyl ester and alkylene oxide in presence of magnesia carrying metal ions as catalyst
    DE4134973A1 (en) * 1991-10-23 1993-04-29 Henkel Kgaa LIQUID CLEANING CONCENTRATE FOR HARD SURFACES
    DE4326112A1 (en) * 1993-08-04 1995-02-09 Henkel Kgaa Detergent for hard surfaces

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    WO1996023049A1 (en) 1996-08-01
    DE19502454A1 (en) 1996-08-01
    EP0805846A1 (en) 1997-11-12
    DE59602436D1 (en) 1999-08-19

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